US6444578B1 - Self-aligned silicide process for reduction of Si consumption in shallow junction and thin SOI electronic devices - Google Patents
Self-aligned silicide process for reduction of Si consumption in shallow junction and thin SOI electronic devices Download PDFInfo
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- US6444578B1 US6444578B1 US09/791,024 US79102401A US6444578B1 US 6444578 B1 US6444578 B1 US 6444578B1 US 79102401 A US79102401 A US 79102401A US 6444578 B1 US6444578 B1 US 6444578B1
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
- H01L21/28518—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table the conductive layers comprising silicides
Definitions
- the present invention relates to a method of forming ohmic contacts for a semiconductor device, and more particularly to a self-aligned silicide process, i.e., salicide process, which substantially minimizes silicon (Si) consumption in shallow junction and thin silicon-on-insulator (SOI) electronic devices.
- a self-aligned silicide process i.e., salicide process, which substantially minimizes silicon (Si) consumption in shallow junction and thin silicon-on-insulator (SOI) electronic devices.
- a TiN/Co film is deposited over the devices and annealed to form cobalt monosilicide over exposed Si regions (i.e., source, drain and gate) of the transistors.
- a selective wet etch is then performed to remove the TiN cap and the non-reacted cobalt left over the oxide or nitride regions.
- the cobalt monosilicide is then annealed to form the cobalt disilicide.
- the final cobalt disilicide formed is 3.5 times thicker than the initial cobalt film deposited and the reaction consumed an even thicker layer of Si (3.6 times the initial cobalt film) so that the surface of the silicide is slightly below the original Si surface.
- NiSi brings other concerns about the processing (that are non-existent with a CoSi 2 process) such as a major reduction in thermal budget after silicidation brought about by both the possible formation of higher resistivity NiSi 2 and the morphological stability of the film.
- a second strategy for limiting substrate and junction consumption is to have a secondary source of Si. This had been proposed and can be done in many different ways. Each prior art method must be consistent with the self-aligned process.
- the Si can be added first to the exposed Si regions alone using selective epitaxy before metal deposition. It can also be deposited simultaneously with the metal in a selective chemical vapor deposition (CVD) process. More recently, it has been suggested that the Si be added during silicidation, after the selective etch of the non-reacted metal.
- the Si is deposited as a blanket film above cobalt monosilicide or the metal-rich silicide.
- the formation of CoSi 2 can at least in part come from the reaction with the top Si film helping in reducing Si consumption of the substrate.
- One object of the present invention is to provide a silicidation process which substantially reduces the amount of Si consumed in the source, drain and gate regions of semiconductor electronic devices during silicidation.
- a further object of the present invention is to provide a self-aligned suicide process (i,e., salicide process) that includes materials and processing steps that are compatible with existing semiconductor device technologies.
- a self-aligned suicide process i,e., salicide process
- An even further object of the present invention is to provide a method of forming an ohmic contact (i.e., a silicide region) that is present on the surface of Si in its lowest resistivity phase.
- An additional object of the present invention is to provide a method of forming ohmic, contacts which does not necessarily increase the thermal budget of the process.
- one method of the present invention includes forming a first layer over a semiconductor wafer including at least exposed silicon-containing areas that are not covered by an insulator.
- the first layer comprises a M—Si G alloy, wherein M is Co, Ni or a combination of Co and Ni, where Si is less than 30 atomic % and Ge is less than 20 atomic %.
- the first layer is subjected to a first annealing step which forms a metal rich silicide phase of Co 2 Si or Ni x Si y over the exposed silicon-containing areas, wherein x and y are integers in which x is greater than y and Ge is partly in solution and partly segregates out of the silicide phase.
- the segregated Ge functions to substantially reduce silicon diffusion from the silicon-containing areas to the silicide during phase transformations in a subsequent second annealing step.
- any ureacted M—Si—Ge-alloy present on the semiconductor wafer is etched and thereafter a blanket layer of Si is formed over the silicide and the semiconductor wafer.
- a second annealing is then performed which converts the metal rich silicide phase into its lowest resistance phase Any remaining non-reacted Si is then removed.
- a method of fob an ohmic contact to a SiGe alloy exposed in an opting trough an insulator includes forming a first blanket layer over a semiconductor wafer including at least an exposed Si—Ge alloy not covered by an insulator.
- the first layer comprises a M—Si alloy, wherein M is Co, Ni or a combination of Co and Ni, and Si is less than 30 atomic %.
- the first layer is then subjected to a first annealing step which forms a metal rich silicide phase of Co 2 Si or Ni x Si y , whew x and y are integers in which x>y.
- the SiGe alloy functions to substantially reduce Si diffusion from the SiGe alloy area to the silicide during phase transformations in a subsequent second annealing step. Any unreacted M—Si alloy present on the semiconductor wafer is then etched away and thereafter a blanket layer of Si Is formed over the silicide and the semiconductor wafer. A second annealing is then performed to convert the silicide into its lowest resistance silicide phase and thereafter any remaining non-reacted Si is removed. Note this aspect of the present invention differs from the previous aspect in that the metal alloy is M—Si, other than M—Si—Ge.
- the first annealing step may form Co monosilicide rather than the metal rich silicide phase of Co.
- the second annealing step converts Co monosilicide to Co disilicide.
- FIGS 1 A- 1 G show the basic processing steps of one method of the present invention wherein an ohmic contact is formed over a silicon-containing area exposed in an opening through an insulator using a M—Si—Ge alloy and a blanket layer of Si.
- FIGS. 2A-2G show the basic processing steps of the present invention wherein an ohmic contact is formed over a SiGe area exposed in an opening through an insulator using a M—Si alloy and a blanket layer of Si.
- FIGS. 3A-3B are X-ray diffraction analysis as a function of temperature for CoSi 2 formation from a pure Co film (A), and from a Co—Si alloy (B) on Si substrates.
- FIGS. 4A-4B are X-ray diffraction analysis as a function of temperature showing the CoSi 2 phase region for a pure Co (A), and Co—Si alloy (B) on Si substrates. Note that FIGS. 4A-4B are same as FIGS. 3A-3B except that the Co 2 Si range is magnified.
- FIGS. 1A-1G illustrate the basic processing steps of the present invention that are employed in forming an ohmic contact to a Si-containing area exposed in an opening through an insulator.
- the ohmic contact is formed utilizing a self-aligned silicide process which includes both a M—Si—Ge alloy and a blanket layer of Si.
- the structure shown in FIG. 1A comprises a semiconductor wafer that includes a Si-containing substrate 10 which has patterned insulator 12 formed therein.
- Suitable Si-containing substrates that can be employed in the present invention include, but are not limited to: single crystal silicon, polycrystalline Si, SiGe, amorphous Si, silicon-on-insulator (SOI) and other like Si-containing substrates.
- the patterned insulator is comprised of any organic or inorganic dielectric material which is well known to those skilled in the art including high-k dielectrics and low-k dielectrics. The type of insulator employed is not critical to the present invention.
- the structure shown in FIG. 1A is fabricated using processing techniques well known to those skilled in the art
- a layer of insulator is formed on the surface of substrate 10 utilizing a conventional deposition process such as chemical vapor deposition (CVD), plasma enhanced CVD, spin-on coating, chemical solution deposition, and other like deposition processes.
- the patterned insulator includes at least one opening 14 which exposes an area of substrate 10 in which an ohmic contact is to be formed.
- the patterned insulator containing the at least one opening is formed by conventional lithography and etching.
- the etching process employed in forming the patterned insulator is highly selective for removing insulator as compared to substrate.
- a thin oxide layer (not shown) may be present on the surface of the substrate prior to, or after formation of the patterned insulator. In embodiments wherein the oxide is not desirable, the oxide may be removed utilizing a wet etch process.
- the Si-containing substrate may be doped or undoped and it may contain various isolation and device regions therein. For clarity, these various regions are not shown in the drawings of the present invention, but are meant to be included within region 10 .
- first layer 16 is formed over the entire semiconductor wafer including the exposed substrate and insulator utilizing a conventional blanket deposition process such as CVD, plasma-assisted CVD, evaporation, sputtering and other like deposition processes. Of these various deposition processes, it is preferred to form first layer 16 by a sputtering process. Alternatively, first layer 16 may be formed by first depositing a metal layer on the semiconductor wafer, and thereafter doping the metal layer with Si and Ge utilizing conventional ion implantation processes well known to those skilled in the art.
- the first layer 16 is comprised of a M—Si—Ge alloy, wherein M is selected from the group consisting of Co, Ni and a combination of Co and Ni. Of the various metals for M, it is preferred in the present invention to form Co-Si—Ge alloys.
- Si is present in the alloy in an amount of less than about 30 atomic % and Ge is present in the alloy in an amount of less than about 20 atomic %. In a preferred embodiment of the present invention, Si is present in the alloy in an amount of from about 15 to about 25 atomic % and Ge is present in the alloy in an amount of from about 2 to about 10 atomic %.
- the M—Si—Ge alloy of the present invention may also include at least one of the following additives: C, Al, Sc, Ti, V, Cr, Mn, Fe, Cu, Y, Zr, Nb, Mo, Ru, Rh, Pd, In, Sn, La, Hf, Ta, W, Re, Ir, Pt, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.
- C, Al, Sc, Ti, V, Cr, Mn, Fe, Cu, Y, Zr, Nb, Mo, Ru, Rh, Pd, In, Sn, La, Hf. Ta, W, Re, Ir, Pt or mixtures thereof are highly preferred, with Ti, V, Cr, Nb, Rh, Ta and Re being more highly preferred.
- the at least one alloy additive is present in an amount of up to about 30 atomic %, with a range of from about 0.1 to about 10 atomic % being more preferred Mixtures of one or more additives is also contemplated herein.
- M—Si—Ge alloy is used herein to denote compositions that have a uniform or non-uniform distribution of Ge and Si therein; compositions that have a gradient distribution of Si and Ge therein; or mixtures and compounds thereof.
- an optional oxygen barrier layer 18 may be formed on the surface of M—Si—Ge alloy (i.e., first layer 16 ).
- the optional oxygen barrier layer is formed using a conventional blanket deposition process well known to those skilled in the art, including, but not limited to: CVD, plasma-assisted CVD, sputtering, plating, spin-on coating and other like deposition processes.
- the thickness of the optional oxygen barrier layer is not critical to the present invention as along as the oxygen barrier layer is capable of preventing oxygen or another ambient gas from diffusing into the structure.
- the optional oxygen barrier layer has a thickness of from about 10 to about 30 nm.
- the optional oxygen barrier layer is composed of conventional materials that are well known to those skilled in the art for preventing oxygen from diffusing into the structure.
- Ti, Si 3 N 4 , TaN, W and other like materials can be employed in the present invention.
- the remaining drawings of the present invention do not depict the presence of the optional oxygen barrier layer, it is possible to employ the method of the present invention when such a barrier layer is present.
- the structure shown in FIG. 1B (or optionally FIG. 1C) is then subjected to a first annealing step so as to convert the M—Si—Ge alloy (i.e., first layer 16 ) into a metal rich silicide phase 20 ; See FIG. 1 D.
- the metal rich silicide phase is comprised of Co 2 Si, or Ni x Si y (where x and y are integers in which x is greater than y) and Ge is partly in solution and partly segregates out of the silicide phase.
- segregated Ge serves to substantially reduce Si diffusion from the Si-containing substrate to the silicide during phase transformations which occur in the second annealing step to be mentioned in greater detail hereinbelow.
- the segregated Ge forms a SiGe interlayer between the Si-containing substrate and the metal rich phase. For clarity the SiGe interlayer is not shown in the drawings.
- the first annealing step may form Co monosilicide instead of the metal rich phase.
- the first annealing step of the present invention is carried out using a rapid thermal anneal (RTA) process using a gas atmosphere such as He, Ar, N 2 or forming gas such as H 2 +N 2 or H 2 +Ar.
- RTA rapid thermal anneal
- the RTA is carried out at a temperature of from about 300° to about 700° C. for a time period of about 300 seconds or less using a continuous heating regime or a ramp and soak heating regime.
- Other temperatures and times are also contemplated herein so long as the conditions chosen are capable of performing the aforesaid functions.
- optional oxygen diffusion barrier and any remaining M—Si—Ge alloy 16 is removed from the structure (See, FIG. 1E) using a conventional etching process that is capable of removing the above mentioned layers.
- the optional oxygen barrier layer and any remaining M—Si—Ge alloy may be removed by utilizing a chemical wet etch process.
- Conventional chemical etchants that are well known to those skilled in the art that are highly selective in removing the optional oxygen barrier layer and the M—Si—Ge alloy as compared to the metal rich silicide phase can be employed in the present invention.
- a suitable etchant that may be employed in the present invention is a mixture of hydrogen peroxide and nitric or sulfuric acid. Other chemical etchants can also be employed so long as they have a high selectivity for removing the optional oxygen barrier layer and M—Si—Ge alloy as compared to the metal rich silicide phase provided in the first annealing step mentioned above.
- Suitable dry etching processes include, but are not limited to: reactive-ion etching (RIE), ion-beam etching (IBE), plasma-etching and other like dry etching processes.
- RIE reactive-ion etching
- IBE ion-beam etching
- plasma-etching plasma-etching and other like dry etching processes.
- the surface of the structure may now be cleaned to remove any oxides, nitrides and carbon present at the surface of the silicide.
- This optional step of the present invention may be carried out with an acid such as HF, hot H 3 PO 4 or an in-situ cleaning process such as sputter etching before proceeding to the next step of the present invention.
- a blanket layer of Si 22 is formed over the metal rich silicide phase provided by the first annealing step, See FIG. 1 F. It is noted that the blanket layer of Si is also formed over patterned insulator 12 .
- the blanket layer of Si is comprised of poly-Si, amorphous Si or any other Si-containing layer which can be used in the next annealing step of the present invention.
- the blanket layer is formed utilizing any conventional blanket deposition process such as CVD or sputtering.
- a second annealing step is then performed to the structure shown in FIG. 1F so as to convert the metal rich silicide phase into a silicide region 24 (See, FIG. 1G) which is in its lowest resistance silicide phase.
- metal rich silicide phase is transformed into one of the following silicide phases: CoSi 2 , Co p Ni (1 ⁇ p) Si 2 where p is greater 0 to less than or equal to 0.5, Co p Ni (1 ⁇ p) Si where p is equal to or greater than 0.5 to less than 1, or NiSi.
- Co p Ni (1 ⁇ p) Si 2 and Co p Ni (1 ⁇ p) Si represent the lowest resistance phases of CoNi that may be formed during the second anneal.
- the value of p may be ⁇ 0.2 from the value given above.
- the second annealing step is carried out at a higher annealing temperature than the first annealing step.
- the second annealing step is also carried out by RTA using one of the previously mentioned gas atmospheres.
- the second annealing step is carried out at a temperature of about 600° to about 900° C. for a time period of about 100 seconds or less using a continuous heating regime or a ramp and soak heating regime.
- Other annealing temperatures and times are also contemplated herein so long the conditions are capable of carrying out the aforementioned transformation from the metal rich silicide phase to the lowest resistance silicide phase.
- the steps of forming a blanket layer of Si and second annealing are performed concurrently. This is accomplished by selecting a substrate temperature during the deposition of the blanket layer of Si wherein silicide phase formation occurs in-situ. Typically, this may occur when a substrate temperature of from about 600° to about 900° C. is employed during the blanket deposition of the Si layer.
- substrate 10 was not previously doped, it can be doped after either the first or second annealing steps using conventional techniques that are well known to those skilled in the art.
- any non-reacted Si is removed from the structure utilizing an etching process which has a high selectivity for removing Si as compared to silicide so as to provide the structure shown in FIG. 1 G.
- One possible etchant that can be employed in this step of the present invention is trimethylammonium hydroxide (TMAH).
- the advantage of the present invention over prior art methods is that during the salicidation process, substantially little or no consumption of substrate 10 occurs.
- the substantial minimization of Si consumption afforded by the inventive method is a result of using both the metal alloy layer and the blanket layer of Si.
- FIGS. 1A-1G employs a M—Si—Ge alloy layer, a Si-containing substrate and a blanket layer of Si.
- the following description with reference to FIGS. 2A-2G employs a Si—Ge alloy as a substrate, a M—Si alloy and a blanket layer of Si.
- substrate 11 is a SiGe alloy or a Si substrate containing a Ge implant
- the above mentioned processes and materials are applicable for this aspect of the present invention.
- a first layer 17 of M—Si alloy wherein M is selected from the group consisting of Co, Ni and a combination of Co and Ni is deposited using the above-mentioned deposition processes.
- M is selected from the group consisting of Co, Ni and a combination of Co and Ni
- the resultant structure is shown in FIG. 2 B.
- Si is present in the alloy in an amount of less than about 30 atomic % and even more preferably Si is present in the alloy in an amount of from about 15 to about 25 atomic %.
- the M—Si alloy of the present invention may also include at least one of the following additives: C, Ge, Al, Sc, Ti, V, Cr, Mn, Fe, Cu, Y, Zr, Nb, Mo, Ru, Rh, Pd, In, Sn, La, Hf. Ta, W, Re, Ir, Pt, Ce, Pr, Nd, Sm, Eu, Gd, Th, Dy, Ho, Er, Tm, Yb and Lu.
- C, Ge, Al, Sc, Ti, V, Cr, Mn, Fe, Cu, Y, Zr, Nb, Mo, Ru, Rh, Pd, In, Sn, La, Hf. Ta, W, Re, Ir, Pt or mixtures thereof are highly preferred, with Ti, Ge, V, Cr, Nb, Rh, Ta and Re being more highly preferred.
- the at least one alloy additive is present in an amount of from up to about 30 atomic %, with a range of from about 0.1 to about 10 atomic % being more preferred. Mixtures of one or more additives is also contemplated herein.
- M—Si alloy is used herein to denote compositions that have a uniform or non-uniform distribution of Si therein; compositions that have a gradient distribution of Si therein; or mixtures and compounds thereof.
- an optional oxygen barrier layer 18 may be formed on the surface of the M—Si alloy (i.e., first layer 17 ).
- the structure shown in FIG. 2B (or optionally FIG. 2C) is then subjected to a first annealing step so as to convert the M—Si alloy into a metal rich silicide phase 20 ; See FIG. 2 D.
- the metal rich silicide phase is comprised of Co 2 Si, or Ni x Si y (where x and y are integers in which x is greater than y).
- a SiGe alloy forms which functions to substantially reduce Si diffusion from the SiGe alloy area into the resultant silicide.
- Ge is partly in solution and partly segregates out of the silicide phase.
- the first annealing step may form Co monosilicide rather than the metal rich phase.
- the first annealing step of the present invention is carried out using the various conditions mentioned hereinabove.
- optional oxygen diffusion barrier and any remaining M—Si alloy 17 is removed from the structure (See, FIG. 2E) using the processing technique mentioned above.
- the surface of the structure is cleaned to remove any oxide, nitride or carbon that may be present therein.
- a blanket layer of Si 22 is formed over the metal rich silicide phase fee provided by the first annealing step, See FIG. 2F.
- a second annealing step using conditions mentioned previously herein is then performed on the structure shown in FIG. 2F so as to convert the metal rich silicide phase into a silicide region 24 which is in its lowest resistance silicide phase.
- any unreacted Si is removed from the structure utilizing an etching process which has a high selectivity for removing Si as compared to silicide so as to provide the structure shown in FIG. 2 G.
- the phase sequence is presented for a bilayer of TiN and pure Co on a Si ( 100 ) substrate annealed at 3° C./second.
- the Co( 002 ) peak can be observed around 52° 2 ⁇ up to 450° C. From 445° C. to about 475° C., the film is in the metal rich phase as shown by the Co 2 Si( 301 )peak at a slightly higher angle (about 52.5°). From 475° C. to about 620° C., two monosilicide peaks are observed at about 53° (CoSi( 210 )) and at about 58.5° (CoSi( 211 )). The transformation to the CoSi 2 is clearly seen by the appearance of the strong CoSi 2 ( 220 ) peak at about 55.5°.
- FIG. 3B By comparison, it is clear in FIG. 3B that when a TiN capped Co 0.75 Si 0.20 Ge 0.05 is annealed, the disilicide formation occurs at a temperature more than 100° C. higher. The same effect is also observed for Co-Ge binary alloys. For the effect of the Si in the Co, it is somewhat difficult to see in FIGS. 3A-3B because of the high intensity of the CoSi 2 peak. The same data as presented in FIGS. 3A-3B is shown in FIGS. 4A-4B with a smaller temperature range (300° C. to about 600° C.) in order to point out the temperature region surrounding the metal rich phase. While for a pure Co film in FIG. 4A, the metal rich phase is present from only about 445° C.
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